N-{N-[N-(1,1-Dimethyl­ethoxy­carbon­yl)-l-leuc­yl]-N-methyl-l-leuc­yl}-N-methyl-l-leucine benzyl ester

Xu, W.J.; Liao, X.J.; Diao, J.Z.; Zhou, L.; Xu, S.H.

doi:10.1107/S1600536808034247

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2178

doi:10.1107/S1600536808034247

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N-{N-[N-(1,1-Dimethylethoxycarbonyl)-L-leucyl]-N-methyl-L-leucyl}-N-methyl-L-leucine benzyl ester

Wen Jie Xu,^a Xiao Jian Liao,^b Jian Zhong Diao,^b Lei Zhou ^b and Shi Hai Xu ^b ^*

^aInstitute of Hydrobiology, Jinan University, Guangzhou, Guangdong 510632, People's Republic of China, and ^bDepartment of Chemistry, Jinan University, Guangzhou, Guangdong 510632, People's Republic of China
^*Correspondence e-mail: txush@jnu.edu.cn

(Received 9 October 2008; accepted 20 October 2008; online 25 October 2008)

The tripeptide title compound, C₃₂H₅₃N₃O₆, synthesized in 80% yield by coupling of N-methyl-L-leucine benzyl ester with tert-butoxycarbonyl-L-leucyl-N-methyl-L-leucine at 273 K, conjugates through two amide linkages and includes two protecting groups: a tert-butyloxycarbonyl group at the C-tip and a benzyl group at the N-tip. A classical intermolecular N—H⋯O hydrogen bond and a weak non-conventional intermolecular C—H⋯O contact connect the molecules, forming layers parallel to (001).

Related literature

For the structure of a related dipeptide, see: Liao et al. (2007 ). For the synthesis of linear peptide fragments of cyclic pentapeptide, see: Xu et al. (2008 ).

Experimental

Crystal data

C₃₂H₅₃N₃O₆
M_r = 575.77
Trigonal, P 3₁ 21
a = 13.9784 (3) Å
c = 30.4763 (15) Å
V = 5157.1 (3) Å³
Z = 6
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 (2) K
0.47 × 0.42 × 0.26 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.965, T_max = 0.981
27507 measured reflections
4232 independent reflections
3541 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.138
S = 1.05
4232 reflections
381 parameters
18 restraints
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O3ⁱ	0.88	2.09	2.923 (3)	157
C2—H2⋯O4ⁱⁱ	0.95	2.57	3.499 (5)	166
C18—H18⋯O5	1.00	2.57	3.560 (4)	163
C9—H9⋯O4	0.99	2.33	3.309 (4)	164
Symmetry codes: (i) $[-x+1, -x+y, -z+{\script{1\over 3}}]$ ; (ii) $[-x+1, -x+y+1, -z+{\script{1\over 3}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034247/si2119sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034247/si2119Isup2.hkl

checkCIF report

Comment top

The title compound (I, Fig. 1) was prepared from the dipeptide Benzyl-2-{[2-(tert-butoxycarbonylamino)-4-methylpentanoyl]methylamino} -4-methylpentanoate, which is an intermediate product in the synthesis of polypeptides (Xu et al., 2008). The bond lengths and angles of (I) are unexceptional and are in good agreement with the corresponding values in the dipeptide structure (Liao et al., 2007). A classic intermolecular N—H···O hydrogen bond (Table 1) and a weak non-conventional C—H···O contact connect the molecules to form layers parallel to (0 0 1).

Related literature top

For the structure of a related dipeptide, see: Liao et al. (2007). For the synthesis of linear peptide fragments of cyclic pentapeptide, see: Xu et al. (2008).

Experimental top

The benzyl in Benzyl-2-{[2-(tert-butoxycarbonylamino)-4-methylpentanoyl] methylamino}-4-methylpentanoate (2 mmol) was removed, dried and dissolved using THF under an atmosphere of nitrogen. A coupling reagent 3-(diethoxy-phosphoryloxy)-3H-benzo[d][1,2,3] triazin-4-one (DEPBT 3 mmol) and diisopropylethylamine (DIPEA) were added successively at 273 K. After 10 min, the amine (2.4 mmol) was added in one portion. The mixture was allowed to stand at room temperature for 12 h. The reactions were monitored using TLC. The reaction was concentrated and it was not necessary to carry out the postproccessing, the material was directly subjected to silica gel column chromatography using n-hexane/acetone (20:1) isocratic elution to give the title compound. Colorless crystals suitable for X-ray analysis grew over a period of a week when the solution was exposed to air.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

N-{N-[N-(1,1-Dimethylethoxycarbonyl)-L-leucyl]- N-methyl-L-leucyl}-N-methyl-L-leucine benzyl ester top

Crystal data top

C₃₂H₅₃N₃O₆	D_x = 1.112 Mg m⁻³
M_r = 575.77	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁21	Cell parameters from 5764 reflections
Hall symbol: P 31 2"	θ = 2.2–26.7°
a = 13.9784 (3) Å	µ = 0.08 mm⁻¹
c = 30.4763 (15) Å	T = 173 K
V = 5157.1 (3) Å³	Block, colorless
Z = 6	0.47 × 0.42 × 0.26 mm
F(000) = 1884

Data collection top

Bruker SMART 1000 CCD diffractometer	4232 independent reflections
Radiation source: fine-focus sealed tube	3541 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 27.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→13
T_min = 0.965, T_max = 0.981	k = −17→17
27507 measured reflections	l = −39→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.076P)² + 1.5629P] where P = (F_o² + 2F_c²)/3
4232 reflections	(Δ/σ)_max < 0.001
381 parameters	Δρ_max = 0.43 e Å⁻³
18 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₃₂H₅₃N₃O₆	Z = 6
M_r = 575.77	Mo Kα radiation
Trigonal, P3₁21	µ = 0.08 mm⁻¹
a = 13.9784 (3) Å	T = 173 K
c = 30.4763 (15) Å	0.47 × 0.42 × 0.26 mm
V = 5157.1 (3) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	4232 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3541 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.981	R_int = 0.032
27507 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	18 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.05	Δρ_max = 0.43 e Å⁻³
4232 reflections	Δρ_min = −0.23 e Å⁻³
381 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2754 (3)	0.1859 (3)	0.23021 (11)	0.0520 (8)
H1	0.3538	0.2238	0.2318	0.062*
C2	0.2238 (4)	0.2413 (3)	0.21488 (13)	0.0598 (10)
H2	0.2666	0.3165	0.2064	0.072*
C3	0.1141 (4)	0.1899 (4)	0.2119 (2)	0.0928 (17)
H3	0.0784	0.2276	0.2010	0.111*
C4	0.0541 (4)	0.0827 (5)	0.2248 (3)	0.130 (3)
H4	−0.0242	0.0461	0.2234	0.156*
C5	0.1050 (4)	0.0259 (4)	0.2399 (2)	0.1001 (19)
H5	0.0617	−0.0496	0.2480	0.120*
C6	0.2170 (3)	0.0782 (3)	0.24319 (12)	0.0505 (8)
C7	0.2703 (3)	0.0129 (3)	0.25971 (12)	0.0519 (8)
H7A	0.2490	−0.0099	0.2906	0.062*
H7B	0.2463	−0.0542	0.2416	0.062*
C8	0.4532 (3)	0.0463 (3)	0.26799 (10)	0.0437 (7)
C9	0.5736 (3)	0.1334 (2)	0.26120 (9)	0.0360 (6)
H9	0.5924	0.1264	0.2301	0.043*
C10	0.6515 (3)	0.1151 (3)	0.29028 (10)	0.0457 (8)
H10A	0.6264	0.0352	0.2910	0.055*
H10B	0.6474	0.1384	0.3206	0.055*
C11	0.7710 (3)	0.1778 (3)	0.27493 (11)	0.0511 (8)
H11	0.7880	0.2533	0.2656	0.061*
C12	0.8493 (4)	0.1908 (5)	0.31243 (15)	0.0809 (14)
H12A	0.8332	0.1177	0.3225	0.121*
H12B	0.8392	0.2308	0.3367	0.121*
H12C	0.9259	0.2323	0.3020	0.121*
C13	0.7895 (4)	0.1226 (5)	0.23608 (13)	0.0694 (12)
H13A	0.7761	0.0493	0.2447	0.104*
H13B	0.8658	0.1675	0.2258	0.104*
H13C	0.7385	0.1149	0.2124	0.104*
C14	0.5605 (3)	0.2723 (3)	0.30884 (9)	0.0432 (7)
H14A	0.6278	0.3280	0.3236	0.065*
H14B	0.5241	0.2056	0.3270	0.065*
H14C	0.5104	0.3015	0.3045	0.065*
C15	0.6162 (2)	0.3192 (2)	0.23346 (9)	0.0321 (6)
C16	0.6491 (2)	0.2951 (2)	0.18839 (8)	0.0298 (5)
H16	0.6844	0.2488	0.1929	0.036*
C17	0.7328 (2)	0.4028 (2)	0.16595 (9)	0.0379 (6)
H17A	0.6977	0.4481	0.1603	0.045*
H17B	0.7961	0.4449	0.1859	0.045*
C18	0.7752 (3)	0.3829 (3)	0.12259 (10)	0.0412 (7)
H18	0.7100	0.3250	0.1061	0.049*
C19	0.8540 (4)	0.3405 (4)	0.12951 (13)	0.0650 (10)
H19A	0.8768	0.3262	0.1010	0.097*
H19B	0.8174	0.2719	0.1465	0.097*
H19C	0.9191	0.3958	0.1455	0.097*
C20	0.8274 (4)	0.4870 (4)	0.09480 (13)	0.0723 (13)
H20A	0.8921	0.5452	0.1100	0.108*
H20B	0.7736	0.5114	0.0899	0.108*
H20C	0.8502	0.4716	0.0665	0.108*
C21	0.4911 (3)	0.2895 (3)	0.14652 (9)	0.0365 (6)
H21A	0.5140	0.3169	0.1166	0.055*
H21B	0.5089	0.3517	0.1662	0.055*
H21C	0.4113	0.2378	0.1471	0.055*
C22	0.5311 (2)	0.1349 (2)	0.14422 (8)	0.0296 (5)
C23	0.4365 (2)	0.0770 (2)	0.11090 (8)	0.0294 (5)
H23	0.4220	0.1331	0.0968	0.035*
C24	0.3335 (2)	−0.0066 (2)	0.13576 (9)	0.0317 (6)
H24A	0.3193	0.0325	0.1597	0.038*
H24B	0.3488	−0.0618	0.1494	0.038*
C25	0.2289 (2)	−0.0677 (3)	0.10791 (9)	0.0378 (6)
H25	0.2416	−0.1116	0.0851	0.045*
C26	0.1327 (3)	−0.1472 (3)	0.13673 (11)	0.0447 (7)
H26A	0.1177	−0.1054	0.1587	0.067*
H26B	0.1517	−0.1978	0.1515	0.067*
H26C	0.0670	−0.1897	0.1185	0.067*
C27	0.2013 (3)	0.0120 (4)	0.08478 (14)	0.0685 (12)
H27A	0.1348	−0.0299	0.0669	0.103*
H27B	0.2632	0.0616	0.0659	0.103*
H27C	0.1882	0.0555	0.1067	0.103*
C28	0.5515 (2)	0.0915 (2)	0.05042 (8)	0.0335 (6)
C29	0.6809 (3)	0.0907 (3)	−0.00321 (9)	0.0383 (6)
C30	0.7820 (3)	0.1894 (3)	0.01674 (10)	0.0512 (8)
H30A	0.7653	0.2483	0.0229	0.077*
H30B	0.8439	0.2164	−0.0039	0.077*
H30C	0.8020	0.1668	0.0441	0.077*
C31	0.7080 (3)	0.0009 (3)	−0.01504 (10)	0.0463 (8)
H31A	0.7347	−0.0194	0.0111	0.069*
H31B	0.7653	0.0285	−0.0377	0.069*
H31C	0.6414	−0.0641	−0.0261	0.069*
C32	0.6356 (3)	0.1225 (3)	−0.04226 (10)	0.0460 (7)
H32A	0.5678	0.0576	−0.0526	0.069*
H32B	0.6905	0.1501	−0.0659	0.069*
H32C	0.6192	0.1803	−0.0336	0.069*
N1	0.5894 (2)	0.24496 (19)	0.26592 (7)	0.0338 (5)
N2	0.54989 (18)	0.23237 (18)	0.16121 (7)	0.0288 (5)
N3	0.46804 (19)	0.02448 (19)	0.07749 (7)	0.0302 (5)
H3A	0.4344	−0.0479	0.0749	0.036*
O1	0.38691 (19)	0.08380 (19)	0.25637 (8)	0.0500 (6)
O2	0.4211 (3)	−0.0461 (2)	0.27986 (13)	0.0891 (11)
O3	0.61650 (19)	0.40624 (17)	0.23920 (6)	0.0398 (5)
O4	0.58401 (17)	0.09059 (17)	0.15495 (7)	0.0391 (5)
O5	0.5840 (2)	0.18927 (17)	0.04605 (7)	0.0438 (5)
O6	0.59298 (17)	0.03485 (17)	0.02975 (6)	0.0362 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0459 (19)	0.056 (2)	0.0467 (17)	0.0203 (18)	0.0047 (15)	0.0046 (15)
C2	0.059 (2)	0.052 (2)	0.067 (2)	0.0271 (19)	−0.0005 (19)	−0.0033 (18)
C3	0.054 (3)	0.055 (3)	0.167 (5)	0.027 (2)	−0.005 (3)	0.003 (3)
C4	0.048 (3)	0.078 (4)	0.262 (8)	0.029 (3)	0.006 (4)	0.030 (4)
C5	0.042 (2)	0.051 (3)	0.198 (6)	0.016 (2)	0.014 (3)	0.022 (3)
C6	0.0374 (17)	0.0439 (19)	0.0607 (19)	0.0131 (15)	0.0018 (15)	−0.0149 (15)
C7	0.0398 (18)	0.0465 (19)	0.0574 (19)	0.0124 (16)	0.0059 (15)	0.0048 (16)
C8	0.0471 (18)	0.0354 (16)	0.0453 (16)	0.0181 (14)	−0.0030 (14)	0.0052 (13)
C9	0.0430 (16)	0.0338 (15)	0.0351 (14)	0.0221 (13)	0.0023 (12)	0.0029 (11)
C10	0.0532 (19)	0.0512 (19)	0.0404 (15)	0.0319 (16)	−0.0035 (14)	0.0060 (14)
C11	0.049 (2)	0.058 (2)	0.0544 (18)	0.0330 (18)	−0.0101 (15)	−0.0005 (16)
C12	0.069 (3)	0.102 (4)	0.082 (3)	0.051 (3)	−0.031 (2)	−0.016 (3)
C13	0.064 (3)	0.108 (4)	0.061 (2)	0.061 (3)	−0.001 (2)	−0.001 (2)
C14	0.0485 (18)	0.0439 (17)	0.0366 (14)	0.0227 (15)	0.0067 (13)	−0.0019 (13)
C15	0.0271 (13)	0.0327 (14)	0.0364 (13)	0.0149 (11)	−0.0039 (11)	−0.0024 (11)
C16	0.0283 (13)	0.0271 (13)	0.0323 (12)	0.0124 (11)	−0.0015 (10)	−0.0013 (10)
C17	0.0357 (15)	0.0317 (15)	0.0385 (14)	0.0110 (13)	0.0037 (12)	−0.0009 (11)
C18	0.0357 (16)	0.0377 (16)	0.0386 (14)	0.0097 (13)	0.0046 (12)	−0.0005 (12)
C19	0.057 (2)	0.085 (3)	0.061 (2)	0.042 (2)	0.0086 (18)	−0.004 (2)
C20	0.082 (3)	0.062 (3)	0.063 (2)	0.028 (2)	0.032 (2)	0.018 (2)
C21	0.0406 (16)	0.0354 (15)	0.0416 (14)	0.0251 (13)	−0.0056 (12)	−0.0046 (12)
C22	0.0279 (13)	0.0303 (13)	0.0304 (12)	0.0144 (11)	0.0036 (10)	0.0015 (10)
C23	0.0293 (13)	0.0294 (13)	0.0310 (12)	0.0157 (11)	0.0008 (10)	−0.0012 (10)
C24	0.0293 (13)	0.0333 (14)	0.0311 (12)	0.0146 (12)	0.0032 (10)	−0.0004 (11)
C25	0.0286 (14)	0.0444 (17)	0.0366 (14)	0.0154 (13)	0.0020 (11)	−0.0058 (12)
C26	0.0306 (15)	0.0423 (17)	0.0557 (17)	0.0141 (14)	0.0047 (13)	0.0026 (14)
C27	0.0367 (18)	0.080 (3)	0.075 (2)	0.0188 (19)	−0.0063 (18)	0.031 (2)
C28	0.0342 (14)	0.0344 (15)	0.0306 (12)	0.0162 (12)	0.0005 (11)	−0.0011 (11)
C29	0.0335 (15)	0.0444 (17)	0.0325 (13)	0.0161 (13)	0.0068 (11)	0.0034 (12)
C30	0.0382 (17)	0.058 (2)	0.0446 (16)	0.0149 (16)	0.0044 (14)	−0.0013 (15)
C31	0.0451 (18)	0.063 (2)	0.0389 (15)	0.0335 (17)	0.0094 (14)	0.0024 (15)
C32	0.0512 (19)	0.053 (2)	0.0362 (15)	0.0282 (17)	0.0038 (14)	0.0045 (14)
N1	0.0375 (13)	0.0324 (12)	0.0321 (11)	0.0179 (11)	0.0019 (10)	0.0012 (9)
N2	0.0291 (11)	0.0259 (11)	0.0325 (10)	0.0146 (9)	−0.0017 (9)	−0.0004 (9)
N3	0.0294 (11)	0.0267 (11)	0.0313 (10)	0.0115 (10)	0.0029 (9)	−0.0022 (9)
O1	0.0342 (12)	0.0387 (13)	0.0714 (15)	0.0139 (10)	0.0029 (11)	0.0066 (11)
O2	0.0613 (19)	0.0446 (16)	0.145 (3)	0.0144 (14)	−0.0121 (19)	0.0392 (18)
O3	0.0495 (13)	0.0329 (10)	0.0424 (10)	0.0247 (10)	0.0024 (9)	−0.0012 (8)
O4	0.0400 (12)	0.0364 (11)	0.0479 (11)	0.0242 (10)	−0.0094 (9)	−0.0083 (9)
O5	0.0502 (13)	0.0315 (11)	0.0461 (11)	0.0176 (10)	0.0135 (10)	0.0055 (9)
O6	0.0374 (11)	0.0361 (11)	0.0362 (9)	0.0191 (9)	0.0109 (8)	0.0039 (8)

Geometric parameters (Å, º) top

C1—C6	1.364 (5)	C18—C20	1.518 (5)
C1—C2	1.377 (6)	C18—H18	1.0000
C1—H1	0.9500	C19—H19A	0.9800
C2—C3	1.331 (6)	C19—H19B	0.9800
C2—H2	0.9500	C19—H19C	0.9800
C3—C4	1.359 (8)	C20—H20A	0.9800
C3—H3	0.9500	C20—H20B	0.9800
C4—C5	1.382 (8)	C20—H20C	0.9800
C4—H4	0.9500	C21—N2	1.473 (3)
C5—C6	1.362 (6)	C21—H21A	0.9800
C5—H5	0.9500	C21—H21B	0.9800
C6—C7	1.524 (5)	C21—H21C	0.9800
C7—O1	1.426 (4)	C22—O4	1.223 (3)
C7—H7A	0.9900	C22—N2	1.355 (3)
C7—H7B	0.9900	C22—C23	1.537 (4)
C8—O2	1.193 (4)	C23—N3	1.447 (3)
C8—O1	1.320 (4)	C23—C24	1.526 (4)
C8—C9	1.520 (5)	C23—H23	1.0000
C9—N1	1.468 (4)	C24—C25	1.530 (4)
C9—C10	1.522 (4)	C24—H24A	0.9900
C9—H9	1.0000	C24—H24B	0.9900
C10—C11	1.522 (5)	C25—C27	1.521 (5)
C10—H10A	0.9900	C25—C26	1.523 (4)
C10—H10B	0.9900	C25—H25	1.0000
C11—C13	1.505 (5)	C26—H26A	0.9800
C11—C12	1.529 (5)	C26—H26B	0.9800
C11—H11	1.0000	C26—H26C	0.9800
C12—H12A	0.9800	C27—H27A	0.9800
C12—H12B	0.9800	C27—H27B	0.9800
C12—H12C	0.9800	C27—H27C	0.9800
C13—H13A	0.9800	C28—O5	1.213 (4)
C13—H13B	0.9800	C28—O6	1.349 (3)
C13—H13C	0.9800	C28—N3	1.351 (4)
C14—N1	1.475 (4)	C29—O6	1.473 (3)
C14—H14A	0.9800	C29—C32	1.516 (4)
C14—H14B	0.9800	C29—C30	1.523 (5)
C14—H14C	0.9800	C29—C31	1.525 (5)
C15—O3	1.227 (3)	C30—H30A	0.9800
C15—N1	1.344 (4)	C30—H30B	0.9800
C15—C16	1.538 (4)	C30—H30C	0.9800
C16—N2	1.470 (3)	C31—H31A	0.9800
C16—C17	1.530 (4)	C31—H31B	0.9800
C16—H16	1.0000	C31—H31C	0.9800
C17—C18	1.529 (4)	C32—H32A	0.9800
C17—H17A	0.9900	C32—H32B	0.9800
C17—H17B	0.9900	C32—H32C	0.9800
C18—C19	1.504 (5)	N3—H3A	0.8800

C6—C1—C2	121.7 (4)	C18—C19—H19C	109.5
C6—C1—H1	119.1	H19A—C19—H19C	109.5
C2—C1—H1	119.1	H19B—C19—H19C	109.5
C3—C2—C1	120.4 (4)	C18—C20—H20A	109.5
C3—C2—H2	119.8	C18—C20—H20B	109.5
C1—C2—H2	119.8	H20A—C20—H20B	109.5
C2—C3—C4	119.0 (5)	C18—C20—H20C	109.5
C2—C3—H3	120.5	H20A—C20—H20C	109.5
C4—C3—H3	120.5	H20B—C20—H20C	109.5
C3—C4—C5	121.2 (5)	N2—C21—H21A	109.5
C3—C4—H4	119.4	N2—C21—H21B	109.5
C5—C4—H4	119.4	H21A—C21—H21B	109.5
C6—C5—C4	120.0 (4)	N2—C21—H21C	109.5
C6—C5—H5	120.0	H21A—C21—H21C	109.5
C4—C5—H5	120.0	H21B—C21—H21C	109.5
C5—C6—C1	117.7 (4)	O4—C22—N2	123.0 (2)
C5—C6—C7	118.6 (4)	O4—C22—C23	119.2 (2)
C1—C6—C7	123.7 (3)	N2—C22—C23	117.7 (2)
O1—C7—C6	106.9 (3)	N3—C23—C24	111.8 (2)
O1—C7—H7A	110.3	N3—C23—C22	109.4 (2)
C6—C7—H7A	110.3	C24—C23—C22	108.0 (2)
O1—C7—H7B	110.3	N3—C23—H23	109.2
C6—C7—H7B	110.3	C24—C23—H23	109.2
H7A—C7—H7B	108.6	C22—C23—H23	109.2
O2—C8—O1	123.6 (3)	C23—C24—C25	115.1 (2)
O2—C8—C9	125.1 (3)	C23—C24—H24A	108.5
O1—C8—C9	111.2 (3)	C25—C24—H24A	108.5
N1—C9—C8	110.8 (3)	C23—C24—H24B	108.5
N1—C9—C10	112.4 (3)	C25—C24—H24B	108.5
C8—C9—C10	112.6 (2)	H24A—C24—H24B	107.5
N1—C9—H9	106.9	C27—C25—C26	110.4 (3)
C8—C9—H9	106.9	C27—C25—C24	111.7 (3)
C10—C9—H9	106.9	C26—C25—C24	109.6 (2)
C9—C10—C11	113.3 (3)	C27—C25—H25	108.3
C9—C10—H10A	108.9	C26—C25—H25	108.3
C11—C10—H10A	108.9	C24—C25—H25	108.3
C9—C10—H10B	108.9	C25—C26—H26A	109.5
C11—C10—H10B	108.9	C25—C26—H26B	109.5
H10A—C10—H10B	107.7	H26A—C26—H26B	109.5
C13—C11—C10	111.5 (3)	C25—C26—H26C	109.5
C13—C11—C12	110.7 (3)	H26A—C26—H26C	109.5
C10—C11—C12	110.7 (3)	H26B—C26—H26C	109.5
C13—C11—H11	107.9	C25—C27—H27A	109.5
C10—C11—H11	107.9	C25—C27—H27B	109.5
C12—C11—H11	107.9	H27A—C27—H27B	109.5
C11—C12—H12A	109.5	C25—C27—H27C	109.5
C11—C12—H12B	109.5	H27A—C27—H27C	109.5
H12A—C12—H12B	109.5	H27B—C27—H27C	109.5
C11—C12—H12C	109.5	O5—C28—O6	125.5 (3)
H12A—C12—H12C	109.5	O5—C28—N3	123.8 (3)
H12B—C12—H12C	109.5	O6—C28—N3	110.7 (2)
C11—C13—H13A	109.5	O6—C29—C32	109.3 (2)
C11—C13—H13B	109.5	O6—C29—C30	111.0 (2)
H13A—C13—H13B	109.5	C32—C29—C30	112.5 (3)
C11—C13—H13C	109.5	O6—C29—C31	102.1 (2)
H13A—C13—H13C	109.5	C32—C29—C31	111.6 (3)
H13B—C13—H13C	109.5	C30—C29—C31	109.9 (3)
N1—C14—H14A	109.5	C29—C30—H30A	109.5
N1—C14—H14B	109.5	C29—C30—H30B	109.5
H14A—C14—H14B	109.5	H30A—C30—H30B	109.5
N1—C14—H14C	109.5	C29—C30—H30C	109.5
H14A—C14—H14C	109.5	H30A—C30—H30C	109.5
H14B—C14—H14C	109.5	H30B—C30—H30C	109.5
O3—C15—N1	121.4 (3)	C29—C31—H31A	109.5
O3—C15—C16	119.4 (2)	C29—C31—H31B	109.5
N1—C15—C16	119.1 (2)	H31A—C31—H31B	109.5
N2—C16—C17	111.3 (2)	C29—C31—H31C	109.5
N2—C16—C15	109.7 (2)	H31A—C31—H31C	109.5
C17—C16—C15	110.4 (2)	H31B—C31—H31C	109.5
N2—C16—H16	108.4	C29—C32—H32A	109.5
C17—C16—H16	108.4	C29—C32—H32B	109.5
C15—C16—H16	108.4	H32A—C32—H32B	109.5
C18—C17—C16	112.5 (2)	C29—C32—H32C	109.5
C18—C17—H17A	109.1	H32A—C32—H32C	109.5
C16—C17—H17A	109.1	H32B—C32—H32C	109.5
C18—C17—H17B	109.1	C15—N1—C9	125.7 (2)
C16—C17—H17B	109.1	C15—N1—C14	117.4 (2)
H17A—C17—H17B	107.8	C9—N1—C14	116.5 (2)
C19—C18—C20	111.1 (3)	C22—N2—C16	117.8 (2)
C19—C18—C17	112.1 (3)	C22—N2—C21	123.3 (2)
C20—C18—C17	110.6 (3)	C16—N2—C21	117.6 (2)
C19—C18—H18	107.6	C28—N3—C23	117.0 (2)
C20—C18—H18	107.6	C28—N3—H3A	121.5
C17—C18—H18	107.6	C23—N3—H3A	121.5
C18—C19—H19A	109.5	C8—O1—C7	119.3 (3)
C18—C19—H19B	109.5	C28—O6—C29	119.8 (2)
H19A—C19—H19B	109.5

C6—C1—C2—C3	−0.7 (7)	C22—C23—C24—C25	176.7 (2)
C1—C2—C3—C4	0.8 (9)	C23—C24—C25—C27	−56.8 (4)
C2—C3—C4—C5	−1.4 (12)	C23—C24—C25—C26	−179.5 (2)
C3—C4—C5—C6	1.7 (13)	O3—C15—N1—C9	172.2 (3)
C4—C5—C6—C1	−1.5 (9)	C16—C15—N1—C9	−8.8 (4)
C4—C5—C6—C7	−179.6 (6)	O3—C15—N1—C14	−0.1 (4)
C2—C1—C6—C5	1.0 (6)	C16—C15—N1—C14	178.8 (2)
C2—C1—C6—C7	179.0 (3)	C8—C9—N1—C15	−111.7 (3)
C5—C6—C7—O1	175.1 (4)	C10—C9—N1—C15	121.2 (3)
C1—C6—C7—O1	−2.9 (5)	C8—C9—N1—C14	60.7 (3)
O2—C8—C9—N1	−154.8 (4)	C10—C9—N1—C14	−66.3 (3)
O1—C8—C9—N1	29.2 (4)	O4—C22—N2—C16	9.8 (4)
O2—C8—C9—C10	−27.9 (5)	C23—C22—N2—C16	−172.0 (2)
O1—C8—C9—C10	156.1 (3)	O4—C22—N2—C21	176.2 (3)
N1—C9—C10—C11	−71.4 (3)	C23—C22—N2—C21	−5.5 (4)
C8—C9—C10—C11	162.6 (3)	C17—C16—N2—C22	112.7 (3)
C9—C10—C11—C13	−76.7 (4)	C15—C16—N2—C22	−124.8 (2)
C9—C10—C11—C12	159.6 (3)	C17—C16—N2—C21	−54.5 (3)
O3—C15—C16—N2	−92.8 (3)	C15—C16—N2—C21	68.0 (3)
N1—C15—C16—N2	88.2 (3)	O5—C28—N3—C23	−16.8 (4)
O3—C15—C16—C17	30.3 (4)	O6—C28—N3—C23	162.6 (2)
N1—C15—C16—C17	−148.7 (3)	C24—C23—N3—C28	173.5 (2)
N2—C16—C17—C18	−62.4 (3)	C22—C23—N3—C28	−66.9 (3)
C15—C16—C17—C18	175.5 (2)	O2—C8—O1—C7	2.9 (5)
C16—C17—C18—C19	−73.4 (4)	C9—C8—O1—C7	178.9 (3)
C16—C17—C18—C20	161.9 (3)	C6—C7—O1—C8	−178.8 (3)
O4—C22—C23—N3	−38.3 (3)	O5—C28—O6—C29	−3.9 (4)
N2—C22—C23—N3	143.3 (2)	N3—C28—O6—C29	176.7 (2)
O4—C22—C23—C24	83.5 (3)	C32—C29—O6—C28	−65.8 (3)
N2—C22—C23—C24	−94.8 (3)	C30—C29—O6—C28	58.8 (4)
N3—C23—C24—C25	−62.9 (3)	C31—C29—O6—C28	175.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3ⁱ	0.88	2.09	2.923 (3)	157
C2—H2···O4ⁱⁱ	0.95	2.57	3.499 (5)	166
C18—H18···O5	1.00	2.57	3.560 (4)	163
C9—H9···O4	0.99	2.33	3.309 (4)	164

Symmetry codes: (i) −x+1, −x+y, −z+1/3; (ii) −x+1, −x+y+1, −z+1/3.

Experimental details

Crystal data
Chemical formula	C₃₂H₅₃N₃O₆
M_r	575.77
Crystal system, space group	Trigonal, P3₁21
Temperature (K)	173
a, c (Å)	13.9784 (3), 30.4763 (15)
V (Å³)	5157.1 (3)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.47 × 0.42 × 0.26

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.965, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	27507, 4232, 3541
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.138, 1.05
No. of reflections	4232
No. of parameters	381
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.23

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3ⁱ	0.88	2.09	2.923 (3)	156.5
C2—H2···O4ⁱⁱ	0.95	2.57	3.499 (5)	166
C18—H18···O5	1.00	2.57	3.560 (4)	163
C9—H9···O4	0.99	2.33	3.309 (4)	164

Symmetry codes: (i) −x+1, −x+y, −z+1/3; (ii) −x+1, −x+y+1, −z+1/3.

Acknowledgements

This work was supported by grants from the National High Technology Development Project (863 Project) (Nos. 2006A A09Z408 GDSFC 06025194, 2005 A30503001, and 2006Z3-E4041), and the National Natural Science Fund (No. 20772048).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liao, X.-J., Xu, W.-J., Xu, S.-H. & Dong, F.-F. (2007). Acta Cryst. E63, o3313. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, W.-J., Liao, X.-J., Xu, S.-H., Diao, J.-Z., Du, B., Zhou, X.-L. & Pan, S.-S. (2008). Org. Lett. 10, 4569–4572. Web of Science CrossRef PubMed CAS Google Scholar

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Volume 64| Part 11| November 2008| Page o2178

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

N-{N-[N-(1,1-Di­methyl­eth­oxy­carbon­yl)-L-leuc­yl]-N-methyl-L-leuc­yl}-N-methyl-L-leucine benzyl ester

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

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organic compounds

N-{N-[N-(1,1-Dimethylethoxycarbonyl)-L-leucyl]-N-methyl-L-leucyl}-N-methyl-L-leucine benzyl ester